Sulfone peroxycarboxylic acids

ABSTRACT

There are disclosed novel, highly stable sulfone peroxycarboxylic acids useful in detergent compositions alone or as bleaching agents which are represented by the formula ##STR1## wherein A and B are organic moieties bonded to the sulfur atom by a carbon atom and at least one of A and B containing at least one ##STR2## group bonded to a carbon atom.

This is a division of application Ser. No. 097,274, filed Sept. 17, 1987now U.S. Pat. No. 4,758,369 which is a continuation-in-part ofapplication Ser. No. 962,592 filed Nov. 3, 1986, now abandoned.

This invention relates to dry, stable bleaches comprising a sulfoneperoxycarboxylic acid having a sulfone group and attached theretoorganic moieties containing at least one peroxycarboxylic acid group.

BACKGROUND OF THE INVENTION

The present invention relates to dry, stable bleaching compositionscomprising a sulfone peroxycarboxylic acid compound having surprisinginherent properties providing active oxygen bleaching performance evenafter long storage periods.

The property possessed by some materials to bleach is known and widelyused to remove discoloration or stains from articles. The behavior andmechanisms by which such bleaching agents perform their functions areonly partially understood. It is known that many colored materialscontain a conjugated chain, that is, a series of double bonds whichalternate with single bonds. If one of the double bonds is eliminatedthe color is usually destroyed. Therefore, an agent which will remove adouble bond linkage may be an effective bleach. A bleaching agent mayalso act on the groups at the end of the chain. Bleaching materials aregenerally categorized as chlorine, hypochlorites, chloramines, hydrogenperoxide and other peroxy compounds, chlorite and chorine dioxide andreducing agents.

One well known category of bleaches comprises active chlorine releasingcompounds. Bleaches in this category, while effective, have thedisadvantages of tending to weaken or degrade fabrics or othermaterials, to react with other components of formulations containingthem, to degrade the colors of many dyed fabrics or other coloredarticles and to cause yellowing of some synthetic or resin treatedfabrics, etc.

The disadvantages of the active chlorine releasing bleaches are largelyovercome by a second known category of bleaches referred to as inorganicoxygen bleaches comprising inorganic active oxygen releasing compounds.Bleaches in this category, while effective, have also exhibitedsignificant disadvantages. For example, inorganic oxygen bleaches suchas hydrogen peroxide, sodium perborate, sodium percarbonate, and thelike, while often possessing good stability properties, all suffer theserious disadvantage that they must be used at a relatively hightemperature such as 85° C. or higher to be optimally effective in theabsence of costly activators. A trend toward lower washing temperaturesrenders them unacceptable for use in many household washing machineswhich are now being operated at water temperatures less than about 60°C. In general, effectiveness at lower temperatures would be advantageousbecause of reduced energy costs, reduced fabric damage or shrinkage,reduced need for sorting out temperature sensitive articles, etc.

To overcome the unsatisfactory low temperature performance of inorganicoxygen releasing compounds, it has been proposed that they be used incombination with so called bleach activators. Generally, these bleachactivators are compounds which react with an inorganic oxygen bleachduring the bleaching operation to release, in situ, a more reactiveoxygen bleach such as a peroxycarboxylic acid. Several seriousdisadvantages are involved in the use of such combinations of inorganicoxygen bleaches with bleach activators. For example, in typical practiceit is necessary to employ a large excess of either the inorganic oxygenreleasing compound or the activator in order to obtain an acceptablycomplete and rapid release of the effective bleaching species. Anotherdisadvantage is that the bleach activator must contain within itsstructure moieties which, upon release of the effective bleachingspecies, become side products. These side products contribute little ornothing to bleaching. Thus, the inclusion of these moieties tends to bewasteful.

All of the above-mentioned disadvantages of chlorine bleaches andinorganic oxygen bleaches used alone or in combination with activatorscan be overcome by the use of effective organic oxygen bleaches,particularly by the use of peroxycarboxylic acids. A number of suchperoxycarboxylic acid bleaches are known in the art. However, theseprior art peroxycarboxylic acids also exhibit some significantdisadvantages. For example, due to their relatively high reactivity,these compounds tend to be difficult to maintain in an undegraded formduring storage of products containing them, prior to their use. In somecases, it is impossible to achieve an acceptable shelf life. In othercases, it is necessary to use expensive stabilization systems which mayconsume large amounts of stabilizing materials. For example, if priorart peroxycarboxylic acid bleaches are incorporated into a completedetergent formulation, stabilization is possible only at substantialextra cost as by encapsulation or other means of ingredient segregation.Examples of prior art teaching the coating technique to isolateperoxycarboxylic acids are U.S. Pat. Nos. 3,847,830 to Williams et al,4,094,808 to Stewart et al and 4,321,301 to Brichard et al.

Other consequences of inherent molecular instability of peroxycarboxylicacids include the need to blend them with components capable ofabsorbing energy during their decomposition in order to prevent violentdecomposition. See for example U.S. Pat. No. 4,100,095 to Hutchins etal. A further disadvantage of some prior art peroxycarboxylic acids is alack of selectivity in their bleaching action. Thus, in such cases, dyeson some colored articles are significantly damaged during bleaching,although usually not to as great an extent as with chlorine bleaches.

Because of the above disadvantages there is a continuing need for newperoxycarboxylic acid compounds, effective in bleaching, which overcomeor reduce the disadvantages recited above for prior art compounds ofthis class.

SUMMARY OF THE INVENTION

There has now been discovered a new class of peroxycarboxylic acidsgenerally described as sulfone peroxycarboxylic acids. The classdescribed herein has been found to be more storage stable and less pronetoward dye damage than similar prior art peroxycarboxylic acids.Particularly surprising is that some members of the class exhibit acombination of a high level of activity for bleaching or stain removal,a high degree of storage stability, and a very low level of damage todyes in colored articles subjected to bleaching. Other advantages ofmany sulfone peroxycarboxylic acids include means of their preparationwhich are unusually efficient, employment of low cost raw materials intheir production, and physical properties which are favorable forefficiently incorporating them in various formulated products.

Sulfone peroxycarboxylic acids in accordance with this invention arerepresented by the following formula: ##STR3## wherein A and B areperoxycarboxylic acid compatible organic moieties, bonded to the sulfuratom by a carbon atom at least one of A and B containing at least one##STR4## group bonded to a carbon atom except that when A is ##STR5## Bis not phenyl and when A is ##STR6## B is not ##STR7##

While not bound by any theory, it appears that the presence of thesulfone group in the sulfone peroxycarboxylic acids has been found tohave the effect of stabilizing the compound such that long storageperiods are now possible without the traditionally expected large lossin active-oxygen.

Although Formula I above indicates only one sulfone group it is obviousthat there are contemplated within the scope of this invention compoundswherein organic moieties A and B may optionally contain one or moreadditional sulfone groups.

As employed herein "peroxycarboxylic acid compatible" means that themoiety or any substituent group thereon does not react with theperoxycarboxylic acid group under normal conditions of storage and useof the claimed bleaches.

The theoretical active oxygen content of the preferred compounds of thisinvention will be above about 5.42 percent. Also particularly preferredcompounds will contain a total of two peroxycarboxylic acid groups, suchgroups being bonded directly to separate aromatic rings. Also preferredcompounds are those wherein one of A and B is a peroxybenzoic acid groupand the other is an alkyl radical whether branched or straight chain,containing from 1 to 10 carbon atoms and more preferably 1 carbon atom.

DETAILED DESCRIPTION OF THE INVENTION

Any number of suitable organic moieties can be employed to provide theintermediate link between the peroxyacid group and the sulfone group.For example, organic moieties may be employed to modify the solubilityof the compound at point of use.

Each of the organic moieties may contain one or more peroxycarboxylicgroups. Alternatively, effective, stable bleaches are provided bycompounds of the present invention wherein only one of the organicmoieties contains a peroxyacid group. In fact, organic moieties A and Bin the above formula may be the same or different. Embodiments of thisinvention wherein there are contained from 1 to 4 peroxycarboxylic acidgroups are preferred and still more preferred are embodiments containing1 or 2 peroxycarboxylic acid groups. Variation of organic moieties A andB allows for tailoring desirable compounds through choice of the organicmoiety to lend specific properties to the molecule. In the preferredembodiment the compounds of this invention possess at least some degreeof water solubility. The solubility of the compounds of this inventionis, of course, modified by pH conditions at point of use such as indetergent baths.

Preferably, organic moieties A and B of the above formula are selectedfrom the group consisting of cyclic, linear or branched alkyl groupscontaining from about 1 to about 16 carbon atoms (more preferably fromabout 2 to about 10 carbon atoms), aryl groups, aromatic heterocyclicgroups, polyaryl groups consisting of from 2 to about 4 annelatedbenzenoid rings, and combinations thereof. Also, organic moieties A andB can be substituted with essentially any peroxycarboxylic acidcompatible group or groups selected from hydroxy, halogen (chloro,bromo, or fluoro), sulfonate, nitro, carboxylic acid, carboxylate saltor ester, phenyl, C₁ -₅ alkoxy (e.g. ethoxy), heteroaryl, sulfone, amineoxide, amide, ester, nitrile and sulfate groups and the like to replacea hydrogen atom attached to the organic moieties A or B. The organicmoieties A and B may not contain substituents which would react readilywith the active oxygen from the peroxyacid group. Common reactive groupsmay include iodides, ketones, aldehydes, sulfoxides, sulfides,mercaptans, amines, reactive olefins, etc.

The groups A and B may contain any number of combinations of aromaticrings, alkyl chains, substituted aromatic rings, and substituted alkylchains provided only that all substituents are stable in the presence ofa ##STR8## group. Preferred substituents are located to provide adequatestability and are selected from the group consisting of chloro, nitro,alkyl, aryl, ester, ##STR9## and amide.

A particularly preferred class of peroxy-acids of this invention isrepresented by the formula ##STR10## wherein X and Y areperoxycarboxylic acid compatible hydrocarbyl groups, at least one of Xand Y being substituted with at least one ##STR11## group except thatwhen X is ##STR12## Y is not phenyl and when X is ##STR13## Y is not##STR14##

Included in this class are compounds of formula II having at least oneof X and Y substituted with two peroxycarboxylic acid groups. Suchsubstitution permits greater active oxygen to be generated per unitmolecular weight.

Another novel class of sulfone peroxycarboxylic acids of this inventioncomprises compounds wherein taken together the organic moieties X and Yform a heterocyclic ring wherein the sulfur atom is the hetero atom.Compounds of this type are represented by the formula ##STR15## whereinthe heterocyclic ring contains at least 4 carbon atoms and n is aninteger from 1 to 4, preferably 1 or 2. The peroxycarboxylic acid groupsare bonded to carbon atoms. Preferably, the heterocyclic ring contains atotal of 4 to 6 carbon atoms although larger heterocyclic rings arecontemplated, i.e., as large as 12 carbon atoms.

Included among the hydrocarbyl moieties X and Y of formula II are alkyl,aralkyl inclusive of cyclic, straight and branched chain radicals, suchas methyl, ethyl, isopropyl, cyclopropyl, cyclohexyl, tertiary butyl,n-butyl and the various forms of amyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, benzyl, phenylethyl, naphthylethyl, tolylethyl,methylbenzyl, phenylbenzyl and the like, aryl groups and alkaryl groupssuch as phenyl, biphenyl, tolyl, xylyl, naphthyl, and the like. It ispreferred that such X and Y groups contain from 1 to 18 carbon atoms.

The novel sulfone peroxycarboxylic acids of this invention are preparedfrom the corresponding carboxylic acids, esters, anhydrides, etc. inconventional manner. In a typical procedure the sulfone precursor isreacted with hydrogen peroxide in an acidic medium such as sulfuric acidor methanesulfonic acid. Isolation of the sulfone peroxycarboxylic acidis performed in the usual manner for recovering solids since most of thenovel sulfone peroxycarboxylic acids of this invention are normallysolid at room temperature.

The desired sulfone carboxylic acid precursors may be formed byoxidation of a corresponding sulfide. This procedure is well known inthe art to be performed with common oxidizing agents such as hydrogenperoxide, oxygen, potassium permanganate, etc.

It is recommended that sulfone carboxylic acid precursors which are notsufficiently soluble in the acidic medium during peroxidation beconverted to the ester form using low molecular weight alkyl alcoholssuch as methyl, ethyl or propyl alcohols. The ester form is often moreeasily peroxidized to the desired sulfone peroxycarboxylic acid. It hasbeen observed that the sulfone group is relatively stable and withstandsvigorous peroxidation procedures.

Other acids useful in the peroxidation reaction include various sulfonicacids and strong acid cation exchange resins. Generally, peroxidation isconducted at temperatures in the range of from about 0° C. to about 75°C. depending upon the reactivity of the precursor and the stability ofthe precursor and the resulting peroxycarboxylic acid.

Generally, it is preferred to employ a stoichiometric excess ofperoxidizing agent and then separate the excess agent afterperoxidation. Any suitable peroxidizing agent may be employed. Hydrogenperoxide is preferred.

Mixtures of sulfone peroxycarboxylic acids with each other and/or withthe corresponding carboxylic acids or esters are included within thescope of this invention. Such mixtures nearly always result whenprecursors containing two or more groups convertible to peroxycarboxylicacid groups (such as --COOH,--COOR where R is lower alkyl and the like)are reacted with hydrogen peroxide to produce a peroxycarboxylic acidcomposition. In such mixtures, it is preferred that a substantialfraction such as 50% or more of the resulting molecules have all suchgroups converted to the peroxy acid group in order to make efficient useof the precursor.

The water solubility of the sulfone peroxycarboxylic acids of thisinvention can be varied in one or more ways known to one skilled in theart. For example, inclusion of a long alkyl chain tends to depress thewater solubility, especially as the number of carbon atoms increases.Also in many cases solubility tends to decrease as molecular weightincreases. In any given series of compounds varying primarily in watersolubility an optimum degree of water solubility will exist and this canbe determined by routine experimentation. In most cases, a relativelylow water solubility, i.e. less than about 1% by weight, is preferredbecause this facilitates efficient separation of the product from excessH₂ O₂ and acid catalysts used during preparation.

Compounds of this invention can be employed in a variety of modes. Notonly can they be employed in dry bleach formulations but also they canbe employed in hard surface cleaners, laundry detergents, and machinedishwashing compositions as well as a wide variety of other compositionsuseful for laundry or other purposes.

The laundry detergent compositions of this invention comprise from about2 percent to about 80 percent of a detergent surfactant, detergentbuilder or mixtures thereof and from about 0.1 percent to about 50percent of the novel sulfone peroxycarboxylic acids of this invention.

Preferably the compositions contain from about 5 percent to about 30percent detergent surfactant, from about 0 percent to about 50 percentdetergent builder and from about 0.5 percent to about 20 percent of thesulfone peroxycarboxylic acids of this invention to give from about 0.05percent to about 3 percent available oxygen.

Suitable detergent compositions and detergent ingredients are disclosedin U.S. Pat. Nos. 4,166,039, 4,157,978, 4,056,481, 4,049,586, 4,035,257,4,019,998, 4,000,080, and 3,983,078 all of which are incorporated hereinby reference. Disclosures of additional ingredients appear in U.S. Pat.Nos. 4,089,945, 3,987,161 and 3,962,418 incorporated herein byreference. Preferably, the compositions are in solid granular orparticulate form and preferably are formulated to prevent reaction ofother ingredients with the active oxygen in the novel sulfoneperoxycarboxylic acids of this invention.

The dry bleach compositions of this invention comprise from about 0percent to about 50 percent detergent surfactant, detergent builder ormixtures thereof and from about 1 percent to about 50 percent of thestable sulfone peroxycarboxylic acids of this invention. Preferably thecompositions contain from about 5 percent to about 30 percent detergentsurfactant, from about 0 percent to about 50 percent detergent builderand from about 0.5 percent to about 25 percent of the sulfoneperoxycarboxylic acids of this invention to give about 0.05 percent toabout 3 percent active oxygen.

In the following examples, which illustrate the invention, andthroughout the specification, parts and percent are by weight unlessotherwise indicated.

EXAMPLE 1

Preparation of 3,3'-sulfonyldipropionic acid (precursor).

To a 5000 mL 4 neck glass reaction flask, equipped with a mechanicalstirrer, alcohol thermometer, dropping funnel, water cooled condenser,and ice bath were charged 416 g of 3,3'-thiodipropionic acid (Aldrich,99%) and 2234 mL of glacial acetic acid. The resulting slurry was mixeduntil uniform and adjusted to 25° C. To the dropping funnel was charged301.5 mL of 30% aqueous H₂ O₂. With agitation, the H₂ O₂ was added overa period of 40 minutes with ice cooling to maintain the temperature inthe range of 29°-32° C. Agitation was continued for another 11 minutes.The resulting homogeneous solution was cooled to 24° C., and all but asmall reactor heel was transferred to a 4000 mL beaker. To the mixturein the beaker 301.5 mL of 30% H₂ O₂ was added rapidly with agitation (notemperature rise observed). The heel in the reactor was heated to reflux(alcohol thermometer replaced with a plug at 50° C.), and the mixture inthe beaker was added to it via the dropping funnel over a period of 39minutes (transfer completed by rinsing with 100 mL glacial acetic acid).Refluxing was continued for another 62 minutes, and the resulting whiteslurry was cooled to 25° C. Excess H₂ O₂ was destroyed by addition of500 mL of 5% aqueous Na₂ SO₃ solution (absence of active oxygenconfirmed with starch-iodide test paper), with cooling to maintain 25°C. The solids were collected by filtration, reslurried in 600 mL water,again collected by filtration, washed on the filter with four 400 mLportions of water, and dried at ambient temperature to constant weight.The product weighed 464.00 g, equivalent to a yield of 94.6% of theorybased upon the amount of 3,3'-thiodipropionic acid used. Analysis by NMRin DMSO-D6 confirmed that the product was 3,3'-sulfonyldipropionic acid,free of detectable amounts of impurities or retained water.

EXAMPLE 2

Preparation of 3-(cyclohexylsulfonyl)propionic acid (a precursor).

To a 1000 mL 4 neck glass reaction flask equipped with a mechanicalstirrer, dropping funnel, thermometer, water cooled condenser, and icebath were charged 100.18 g of cyclohexylmercaptan and 1 mL of 40%aqueous benzyltrimethylammonium hydroxide solution (as catalyst). To thedropping funnel was charged 84.15 mL (10% excess) of methyl acrylate.With agitation and ice cooling the methyl acrylate was added over aperiod of 14 minutes at 28°-38° C. Following the addition, the ice bathwas replaced by a heating mantle, and agitation was continued at 30±1°C. for 69 minutes. 171.1 mL of 20% aqueous NaOH was charged to thedropping funnel, and 278 mL of absolute ethanol was charged to thereactor. The NaOH (10% excess over methyl acrylate) was added over aperiod of 9 minutes, the temperature rising to 46.5° C. The mixture washeated to reflux (80° C.) and refluxed for 46 minutes. The mixture wascooled to 25° C. and transferred (with H₂ O rinse) to a rotaryevaporator. Using aspirator vacuum and a bath temperature of 50°-55° C.,280 mL of volatile material (mostly ethanol) was stripped off anddiscarded. The residue was a homogeneous, water white solution weighing360.3 g. The residue was cooled in an ice bath, transferred to a 1000 mLseparatory funnel, and reacted therein with 95.8 mL of cold 37% aqueousHCl (10% excess over NaOH). Enough dry NaCl was added in severalportions to nearly saturate the aqueous phase. After cooling, shaking,and settling for 30 minutes, the mixture consisted of an upper oil phasecontaining the bulk of the product and a lower aqueous phase which wasdrained off and discarded. The oil phase was washed once with an equalvolume of nearly saturated aqueous NaCl, and after settling overnight,the wash layer was drained off and discarded. The oil phase wastransferred to a 2000 mL 4 neck glass reaction flask, fitted with adropping funnel, mechanical agitator, alcohol thermometer, refluxcondenser, and an ice bath. 860 mL of glacial acetic acid was alsocharged, part of it being used to rinse residues from the separatoryfunnel into the reactor. To the dropping funnel was charged 133.3 mL of30% H₂ O₂ (50% excess over theoretical for conversion to the sulfoxide).The H₂ O₂ was added with agitation over a period of 22 minutes withcooling as needed to maintain ≦32° C. Following the addition, agitationwas continued without cooling for 68 minutes, the temperature decliningto 25.5° C. Leaving a small heel in the reactor, most of the reactionmixture was transferred to a 4000 mL beaker and mixed with another 133.3mL of 30% H₂ O₂ (no temperature rise observed). The heel was heated toreflux, and the mixture from the beaker was added to the reactor via thedropping funnel over a period of 37 minutes. Refluxing was continued foranother 60 minutes, and the mixture was then cooled to room temperature.Another 102 mL of 30% H₂ O₂ was added and mixed in, and the mixture wasallowed to stand for 41/2 days at ambient temperature. Excess H₂ O₂ wasdestroyed by mixing with 900 mL water and 219.18 g Na₂ SO₃ in a 4000 mLbeaker at ≦50° C. The liquid phase was separated from undissolved saltsby a combination of decantation and filtration and transferred to arotary evaporator (in several batches) where volatiles were stripped offat a bath temperature of 51°-52° C. (aspirator vacuum) and discarded.The residue, a thin sludge, became a solid crystalline mass upon coolingand standing. The total product was collected in a 4000 mL beaker anddiluted with water to 1000 mL. This mixture was heated to 80° C., atwhich temperature it was a homogeneous solution. It was then cooled to18° C., at which temperature it crystallized rapidly to form a thickwhite slurry. The solids were collected by filtration at 15°-20° C.,washed on the filter with water, and dried at ambient temperature toconstant weight. The product weighed 129.12 g, equivalent to a yield of68% of theory based upon the amount of cyclohexylmercaptan used.Analysis by NMR in DMSO-D6 confirmed that the product was3-(cyclohexylsulfonyl)propionic acid, free of detectable amounts ofimpurities or retained water.

EXAMPLE 3

Preparation of 4,4'-sulfonyldiperoxybenzoic acid.

The starting material was sulfonyldimethylbenzoate, ground to a powderusing a mortar and pestle prior to weighing. To a 400 mL beaker,equipped with a support clamp, heating mantle, thermowell andthermocouple, dropping funnel, and glass and teflon mechanical stirrer,were charged 34.4 g (0.103 mole) of the above powder and 100 mL of 99.5%methanesulfonic acid. After a few minutes mixing at ambient temperature,a uniform slurry was obtained. To the dropping funnel was charged 16.8mL of 90% aqueous H₂ O₂ (0.618 mole, 3 fold excess). The slurry in thebeaker was heated to 57° C., and the H₂ O₂ was added dropwise over aperiod of 37 minutes with agitation. The temperature rose to the range58°-60° C. and was then maintained there throughout the addition byadjustment, of heat input. Following the addition, agitation wascontinued for 183 minutes at 58°-62° C. The mixture remained a whiteslurry throughout the reaction. The mixture was then cooled to 10° C.and filtered. The solids were redispersed in 300 mL of cold (5° 10° C.)pH 5 phosphate buffer solution (prepared by titration of 10% aqueousNaOH to pH 5.0 with 85% H₃ PO₄). The solids were again collected byfiltration and redispersed into 100 mL of cold (5°-10° C.) water. Thesolids were again collected by filtration and redispersed with 26.1 gpowdered boric acid (99.78% H₃ BO₃) and 100 mL cold (5°-10° C.) 1.96%aqueous boric acid solution. The solids were collected by filtration anddried on a sheet of glass at ambient temperature to constant weight. Thedried product weighed 56.32 g. Active oxygen content was determinedtwice (iodometric titration) obtaining results of 3.71% and 3.73%. Theactive yield was 63.64% of theory (for complete conversion to thediperacid), calculated as follows: ##EQU1##

It is estimated that the product contained about 46.34% boric acid,based upon the amount of powdered boric acid charged. Thus, the activityof the organic fraction was about 3.72/0.5366=6.933%, which is 73.29% ofthe theoretical 9.46% for the pure diperacid. This activity is equal tothat of a mixture consisting of 43.8% 4,4'-sulfonyldiperoxybenzoic acidand 56.2% 4,4'-sulfonylmonobenzoic monoperoxybenzoic acid.

Throughout the above procedure, the only equipment contacting thereaction mixture or product consisted of porcelain, Teflon®, glass, orpolyethylene. Filtrations employed vacuum and used glass microfibrefilter media.

EXAMPLE 4

Preparation of 3-(cyclohexylsulfonyl)peroxypropionic acid.

To a 150 mL beaker equipped with a support clamp, ice bath, alcoholthermometer, mechanical stirrer, and dropping funnel were charged 22.03g (0.1 mole) of powdered 3-(cyclohexylsulfonyl)propionic acid and 29.8mL of 82 wt. % aqueous H₂ SO₄. After a few minutes mixing at ambienttemperature, a uniform slurry was obtained. To the dropping funnel wascharged a solution prepared by adding 33.3 mL of 95.5% H₂ SO₄ to 17.0 mLof 50% H₂ O₂ (0.3 mole, 3 fold excess) with stirring and cooling tomaintain ≦30° C., with final cooling to 25° C. With agitation, themixture in the dropping funnel was added to the beaker over a 10 minuteperiod, the temperature rising to 27° C. The ice bath was not appliedbecause the heat evolution was so small. The mixture was agitated foranother 130 minutes, the temperature gradually declining to 26.5° C.Most of the solids dissolved. The mixture was then contacted with ten25-30 mL portions of methylene chloride at ambient temperature in aneffort to recover the product by direct extraction into the methylenechloride. The combined extracts were washed with pH 5 phosphate buffersolution, then washed with water, partially evaporated, mixed with aweighed amount of boric acid, and dried. The weight and active oxygenanalysis of this product showed that only 3.57 g of the organic producthad been recovered by extraction (˜15% of theory) and that its activitywas 91.1% of that for the pure peracid. The crude reaction productremaining after methylene chloride extraction was mixed with 100 mL ofcold pH 5 buffer with agitation and ice cooling, resulting in immediateformation of a large amount of white solids. The slurry was filtered at15°-20° C. and the solids were washed on the filter with two 100 mLportions of cold buffer followed by 100 mL cold water. The resultingproduct was mixed with boric acid and dried and then blended uniformlywith most of the product recovered by extraction. The resulting finalproduct weighed about 30 g and had an active oxygen content of 3.27%(boric acid content roughly 47%). The calculated active yield was 61% oftheory. (Equipment, analysis, and yield calculation were as described inExample 3.)

EXAMPLE 5

Preparation of 3,3'-sulfonyldiperoxypropionic acid.

A stirred mixture of 100 g of 3,3'-sulfonylbispropionic acid and 600 mLof methanesulfonic acid (99.5% purity from Alfa) in a one liter beakerwas heated to 35° C. in a heated water bath. Heating was then stoppedand 107 g of 90% hydrogen peroxide was then added dropwise via a pipetteover approximately one hour. During the addition of the hydrogenperoxide, the temperature of the reaction mixture rose to a temperatureranging between 40° C. and 45° C. After the addition of the hydrogenperoxide was completed, the stirred reaction mixture was kept atapproximately 40° C. for two hours. Throughout this procedure thereaction mixture had two phases, a solid phase and a liquid phase.Heating was stopped and the reaction mixture was cooled to approximately10° C. in an ice bath. The solid-liquid mixture was then poured onto iceprepared from deionized water. The solid was filtered from solutionusing a coarse sintered-glass funnel. The solid was then washed fourtimes with cold, deionized water. For each of the washings the solid wastransferred from the funnel to a beaker, was slurried with approximately500-600 mL of cold deionized water and was filtered away from thesolution using the coarse sintered-glass funnel. The solid wastransferred to a watchglass and dried overnight. The dried productweighed 95.1 g which is a yield of 82.5% of theoretical based upon theweight of starting sulfone carboxylic acid. On the basis of an averageof two titrations the product contained 13.12% available oxygenrepresenting 99.3% of the theoretical value.

Stabilization with Boric Acid

The product was mixed with an equal weight of boric acid powder. Thismixture was put through a #30 polyethylene sieve. Particle size would be<600 microns. The mixture was then bottled and the bottle was shaken toblend well the boric acid with the product.

Percent active oxygen in the boric acidstabilized product was found tobe 6.68%.

EXAMPLE 6

Preparation of 4-(methylsulfonyl)benzoic acid (a precursor)

A mixture of 5 g of 4-(methylthio)-benzoic acid (97%) and 30 mL ofglacial acetic acid was formed. The mixture was cooled in a water bathcontaining a small amount of ice. To the mixture was added 8.5 g of30hydrogen peroxide gradually over one hour. No temperature rise wasobserved during the addition of the hydrogen peroxide. The reactionmixture was then heated for one and a half hours with the temperatureranging between 70° C. and 100° C. Heating was stopped and the reactionmixture was allowed to cool to room temperature. A solid was present inthe reaction mixture. A solution of 3 g of sodium sulfite in 57 g ofwater was added to the reaction mixture. The solid was filtered fromsolution and was washed three times with cold deionized water. The solidwas transferred to a watchglass and dried overnight. The dried productweighed 5.25 g which is a yield of 88.1% of the theoretical based uponthe amount of the starting benzoic acid.

An NMR spectrum of the product in deuterated dimethylsulfoxide was inagreement with a literature spectrum of the compound in the same solvent("Aldrich Library of NMR Spectra").

This batch of product was combined with the product from a larger scalebatch (4x). The combined products were recrystallized from ethanol. Therecrystallized material was used in the synthesis of4-(methylsulfonyl)peroxybenzoic acid.

EXAMPLE 7

Preparation of 4-(methylsulfonyl)peroxybenzoic acid.

A stirred mixture of 5 g of 4-(methylsulfonyl)benzoic acid and 50 mL ofmethanesulfonic acid froze when it was cooled in an ice bath. The icebath was removed and when the mixture was partially melted, stirring wasresumed and the addition of 2.83 g of 90% hydrogen peroxide was started.The 90% hydrogen peroxide was added gradually over ten minutes. When theaddition of the hydrogen peroxide was completed, the reaction mixturewas still partially frozen. A water bath of cold tap water was used towarm the reaction mixture. The temperature of the reaction mixture rosebriefly to 28° C. One hour after the addition of the hydrogen peroxidewas started, the reaction mixture was heated for 70 minutes within atemperature range of 40° C.-45° C. The stirred reaction mixture was thencooled in an ice bath. A solid precipitated from solution. When thetemperature of the reaction mixture was between 10° C.-15° C., the solidproduct was filtered from solution. A second fraction of solid productwas collected when the filtrate was poured onto ice prepared fromdeionized water and the solid which formed was filtered away fromsolution. Fraction one was washed four times with 60 mL each time ofcold deionized water. Fraction two was washed four times with 150 mLeach time of cold deionized water. Both fractions of the solid productwere very easy to wash and to isolate by filtration. The two fractionswere each transferred to a watchglass and dried overnight. The driedsolids were fine, dry powders.

    ______________________________________                                                           Fraction 1                                                                            Fraction 2                                         ______________________________________                                        Weight of product:    3.3331 g  1.0836 g                                      (The combined weights would represent                                         a yield of 81.8% of the theoretical                                           5.4 g).                                                                       Percent by weight of active oxygen:                                                                 6.67      6.54                                          Percent of theoretical active oxygen:                                                              90.1      88.4                                           Melting point:       154.5-156° C.                                     ______________________________________                                    

Stabilization with boric acid

The two fractions were combined and an equal weight of boric acid powderwas added. The mixture was put through a #30 polyethylene sieve.Particle size would be <600 microns. The mixture was then bottled andthe bottle was shaken to blend well the boric acid with the product.

Percent by weight of active oxygen in the boric acid-stabilized productwas 3.31%.

EXAMPLE 8

Preparation of 11-mercaptoundecanoic acid (a precursor).

A mixture of 200 g of 11-bromoundecanoic acid, 60 g of thiourea and 600mL of absolute ethanol was stirred and heated at reflux for two hours.After heating was stopped a solution of 80 g of sodium hydroxide in 250mL of water was then added dropwise. The mixture was held overnight andthen heated at reflux for three hours. After cooling to room temperaturea solid precipitated from solution. The reaction mixture was poured intoa mixture of ice and 200 g of concentrated hydrochloric acid. The solidswere filtered from solution then slurried with ice water, isolated byfiltration and washed twice. The off-white solid was stored in acrystallizing dish for one week, then dried under vacuum (˜1 mm of Hg)at about 45° C. The product was distilled under vacuum (˜1 mm of Hg at˜160° C.). NMR analysis indicated the desired product was obtained. Thedistilled product weighed 74.7 g representing 45.46% yield based uponthe weight of starting 11-bromoundecanoic acid.

EXAMPLE 9

Preparation of 11-(methylthio)undecanoic acid (a precursor).

Into a 3-neck round-bottom flask fitted with a condenser and an additionfunnel were added 20 g of 11-mercaptoundecanoic acid, 13 g of methyliodide and 200 mL of ethanol. A slow flow of nitrogen through thereactor was started to exclude oxygen because mercaptans can beconverted into disulfides in the presence of air and strong alkali. Asolution of 7.33 g of sodium hydroxide in 14.66 g of water was addeddropwise to the reaction mixture via the addition funnel. The reactionmixture was kept at room temperature overnight. Any unreacted methyliodide, the ethanol and the water were removed using a rotovap. Theresidue was acidified using a mixture of concentrated hydrochloric acidand ice. After isolation the product was distilled. After a small amountof a low boiling fraction was collected, the desired product wascollected at ˜1 mm of Hg at 180° C. weighing 22.75 g. The crude productwas distilled to yield 12.5 g of desired product representing 58.7% oftheoretical based upon the weight of starting 11-mercaptoundecanoicacid.

EXAMPLE 10

Preparation of 11-(methylsulfonyl)undecanoic acid (a precursor).

Into a three-neck round-bottom flask fitted with an overhead mechanicalstirrer, thermometer and addition funnel were added 12.3 g of11-(methylthio)undecanoic acid and 53 mL of acetic acid. The mixture waswarmed slightly to help all of the solid to dissolve in the acetic acid.At a temperature of approximately 30° C., the dropwise addition of 24 gof 30% hydrogen peroxide was started. After the addition was completed,the reaction mixture was stirred without heating for an hour. Themixture was then heated at slow reflux or an hour. The reaction mixturewas cooled first to room temperature and then in an ice bath. Aqueoussodium sulfite (5%) was added to decompose all active oxygen present.The solid was filtered and washed several times with cold deionizedwater. The solid was then dried overnight on a watchglass. The productweighed about 7.7 g (55% of theoretical) based upon the weight ofstarting acid.

EXAMPLE 11

Preparation of 11-(methylsulfonyl)peroxyundecanoic acid.

A stirred mixture of 3 g of 11-(methylsulfonyl)undecanoic acid and 30 mLof methanesulfonic acid was heated to approximately 40° C. The soliddissolved only partially in the methanesulfonic acid at thistemperature. Then 1.29 g of 90% hydrogen peroxide was added dropwise.The temperature of the reaction mixture was reduced to room temperatureafter twenty minutes of reaction time. For the remainder of the two hourreaction time, the reaction mixture was not heated and becamehomogeneous. The reaction mixture was then cooled in an ice bath forminga solid which was then filtered from solution. The filtrate was pouredonto ice prepared from distilled water. A solid formed which wasfiltered from solution. The two solids collected were combined andwashed several times with cold deionized water until the filtrate was nolonger strongly acidic. The solid was dried overnight on a watchglass,weighed 2.91 g and had 4.8% by weight active oxygen (84.1% oftheoretical).

EXAMPLE 12

Preparation of 3-(n-decylthio)propionitrile (a precursor).

To a 250 mL round-bottomed flask fitted with an overhead mechanicalstirrer, a thermometer and an addition funnel were charged 87 g of1-decanethiol and 20 drops of a 21% by weight solution of sodiumethoxide in ethanol. The mixture was cooled to 10° C. using an ice bath.Then the dropwise addition of 53 g of acrylonitrile was started. Afteraddition of a portion of the acrylonitrile, 10 drops of 21% by weightsolution of sodium ethoxide in ethanol were added. The temperature ofthe reaction mixture during the addition of the remaining acrylonitrileranged between 30° C. and 35° C. The reaction mixture was then kept atroom temperature overnight (˜19 hours). The unreacted acrylonitrile wasthen removed by distillation at atmospheric pressure. The remainingmaterial was then distilled at ˜1 mm pressure. A first fraction wascollected from 150° C. to 160° C. Fraction one had a strong odor ofthiol. A second and final fraction was collected at 160° C. The secondfraction had a faint odor of thiol. An NMR spectrum indicated the secondfraction to be the desired product 83.5% of theoretical (94.9 g) basedupon the weight of 1-decanethiol employed.

EXAMPLE 13

Preparation of 3-(n-decylsulfonyl)peroxypropionic acid.

The product of Example 12 was converted to the corresponding carboxylicacid by alkaline hydrolysis followed by acidification and then to thecorresponding sulfone carboxylic acid by oxidation in accordance with aprocedure found in U.S. Pat. No. 3,857,875 to Brady et al. A stirredmixture of 5 g of 3-(n-decylsulfonyl)propionic acid and 50 mL ofmethanesulfonic acid was heated to 40±3° C. The3-(n-decylsulfonyl)propionic acid dissolved only partially in themethanesulfonic acid at this temperature. Then 2.04 g of 90% hydrogenperoxide was added dropwise via pipette over ten minutes. Before theaddition of the hydrogen peroxide was completed, the reaction mixturebecame thick from precipitation of a solid. After the addition of the90% hydrogen peroxide was completed, the heating of the reaction mixturewas continued at 40±3° C. until the reaction time totalled ninetyminutes beginning at the start of the addition of the hydrogen peroxide.The reaction mixture was then cooled in an ice bath at 10° C. The solidwas then filtered from solution using a coarse sinteredglass funnel,then transferred to a beaker containing 200 mL of ice water preparedfrom deionized water. The product was washed twice with ice water,filtered and dried to provide 4.63 g of the desired product (87.6% oftheoretical based upon the weight of starting3-(n-decylsulfonyl)propionic acid). The product was found to have 5.32%active oxygen. The product was stabilized with an equal weight of boricacid and put through a #30 polyethylene sieve which provided a particlesize of less than 600 microns. The stabilized product contained 2.58% byweight active oxygen.

EXAMPLE 14

Preparation of Sulfonyldiperoxyacetic Acid.

A mixture of 16.32 mL of 90% aqueous hydrogen peroxide (0.6 mole), 2.3mL of deionized water and 18.17 mL of 95.5% sulfuric acid was formed ina 150 mL beaker equipped with an ice bath, alcohol thermometer andmechanical stirrer. The water and sulfuric acid were added sequentiallyto the H₂ O₂ with cooling and stirring to hold the temperature of themixture to about 25° C. This mixture was added to 18.215 g (0.1 mole) ofsulfonyldiacetic acid in admixture with 100 mL of methylene chloridewithout cooling over a period of about 8 minutes with agitation. Theresulting combination formed two liquid phases and one solid phase.Agitation of this mixture was continued for three hours with thetemperature in the range of 20°-22° C. under cover to reduce loss ofmethylene chloride. The mixture was then cooled to about 5° C. anddiluted with 18 mL of deionized water added gradually with stirring andcooling. The solids were collected, reslurried with methylene chlorideand treated with 80 mL of 6% aqueous sodium bicarbonate. The solids werecollected and similarly treated with another 40 mL of 6% NaHCOsresulting in a final pH of about 4. The recovered solids appearedreduced by the reslurry operations and were combined with 2.91 g of drypowdered boric acid. The mixed solids were dried to constant weight(5.24 g) and found to have an active oxygen content of 5.03%.

It was estimated that the organic fraction of the product contained atleast 55% diperacid, plus a considerable amount of the monoperacid.

EXAMPLE BLEACHING PERFORMANCE

In all of the tests below a detergent is employed as a control at a uselevel of 1.5 g/L of wash solution. Various bleach compounds of thisinvention were added to portions of the detergent composition in theamounts shown below in the tables. Each test series contained a control.The detergent formulation is as follows:

    ______________________________________                                        Ingredient          Weight %                                                  ______________________________________                                        Sodium alkyl benzene sulfonate                                                                    16                                                        Sodium carbonate    10                                                        Sodium silicate (47% solids)                                                                       9                                                        Water                8                                                        Carboxymethyl cellulose                                                                            1                                                        Sodium sulfate      24                                                        Sodium tripolyphosphate                                                                           32                                                        ______________________________________                                    

All of the examples below were conducted at the same wash conditions of100° F. and with water having a hardness level of 150 ppm (3:2 moleratio of calcium to magnesium calculated as calcium carbonate). In eachtest a set of three swatches were evenly stained. After staining, thelight reflectance value (Rd_(i)) was measured using the Gardner XL-23Tristimulator Colorimeter manufactured by Gardner Laboratory, Inc.,Bethesda, Md.

A Terg-o-tometer was employed to test the bleaching performance of thebleach compounds. In each test three stained swatches together withthree unstained swatches were placed in a cylindrical container with 1liter of water and 1.5 g of detergent together with a weighed amount ofa bleach compound of this invention. Two minutes were allowed for thedetergent to dissolve. The washing operation covered a period of 10minutes after which the laundered swatches were rinsed with clear waterand dried. Light reflectance measurements of each cleaned dried swatchwere made and averaged (Rd_(f)). The difference (ΔRd) of these readingsfor each type of stain is reported in the tables below. (ΔRd=Rd_(f)-Rd_(i))

The bleach compounds employed in the following examples are representedby the following structure wherein A and B are defined in the tablesbelow. ##STR16##

The tests in Tables I and II below are separate and each includes acontrol result. In some instances compounds of this invention employedin the separate tests were prepared at different times and in smallamounts. The results of each test are comparable only within the contextof the individual tests with control data unless otherwise noted. InTables I and II below the fabric type and kind of stain are listed atthe top of each column of data. The notation of poly/cotton means afabric blend having a ratio of 50:50 of polyester and cotton.

In addition to ΔRd data there is reported in the Tables below thepercent soil removal (%SR) which may be related to visual effect.Percent soil removal reported in the Tables below was calculatedaccording to the formula: ##EQU2## wherein Rd_(i) is the reflectancedata obtained by measuring the reflectance of the test swatches afterstaining but before bleaching in accordance with the procedure describedabove.

                                      TABLE I                                     __________________________________________________________________________                                        poly/cotton                                                                          cotton cotton                                                g/L ppm avail                                                                           coffee grass  wine                        A            B            bleach                                                                            oxygen                                                                              % SR                                                                              ΔRd                                                                        % SR                                                                              ΔRd                                                                        % SR                                                                              ΔRd               __________________________________________________________________________    Control                   --   0    18.0                                                                               8.3                                                                             41.0                                                                              15.5                                                                             19.0                                                                              10.2                     ##STR17##                                                                                  ##STR18##   .2516                                                                             8.00  29.0                                                                              13.4                                                                             52.5                                                                              19.5                                                                             39.7                                                                              21.7                     ##STR19##                                                                                  ##STR20##   .2051                                                                             8.00  37.9                                                                              17.8                                                                             59.8                                                                              22.3                                                                             37.5                                                                              20.5                     ##STR21##                                                                                  ##STR22##   .1207                                                                             8.00  21.5                                                                               9.7                                                                             46.4                                                                              16.9                                                                             29.0                                                                              15.7                    (CH.sub.2).sub.9 CH.sub.3                                                                   ##STR23##   .3101                                                                             8.00  44.9                                                                              20.1                                                                             71.8                                                                              26.9                                                                             34.2                                                                              18.7                    CH.sub.3                                                                                    ##STR24##   .2439                                                                             8.00  29.4                                                                              13.1                                                                             50.2                                                                              19.0                                                                             44.2                                                                              24.0                    __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________                                     cotton cotton cotton                                                g/L ppm avail                                                                           wine   clay   grass                          A          B           bleach                                                                            oxygen                                                                              % SR                                                                              ΔRd                                                                        % SR                                                                              ΔRd                                                                        % SR                                                                              ΔRd                  __________________________________________________________________________    Control                --   0    20.2                                                                              11.1                                                                             37.9                                                                              17.3                                                                             28.5                                                                              11.0                        ##STR25##                                                                                ##STR26##  .1501                                                                             8.00  27.7                                                                              15.1                                                                             41.3                                                                              18.5                                                                             31.0                                                                              12.1                       CH.sub.3                                                                                  ##STR27##  .3150                                                                             8.00  41.1                                                                              22.4                                                                             41.1                                                                              18.5                                                                             44.6                                                                              17.4                        ##STR28##                                                                                ##STR29##  .2072                                                                             8.00  38.7                                                                              21.4                                                                             55.9                                                                              25.0                                                                             43.4                                                                              16.6                       Dodecanediperoxoic Acid*                                                                             .1468                                                                             8.00  34.7                                                                              19.0                                                                             57.7                                                                              25.9                                                                             41.6                                                                              16.0                       __________________________________________________________________________     *known prior art bleach                                                  

EXAMPLE 16 STABILITY TESTS

Improved stability of the compounds of this invention are shown byseveral test procedures described below. In one such test a value "t₅₀ "is determined which is a measure of the amount of time required for ableach compound to lose 50% of its originally determined amount ofactive oxygen. This value is measured for peroxyacids and formulationsthereof by incubating the samples in open glass vials at 39° C. and 85%relative humidity. At periodic intervals, aliquot samples are taken andpercent active oxygen (%AO) is measured by iodometric titration.

A plot of A/Ao versus time where A=%AO @t=incubation time and A0=%AO@t=0generates a curve which shows the decomposition of the peracid. Sincemost organic peracids decompose via an accelerating autocatalytic route,storage stability is reported as "t₅₀ ".

Data for several of the sulfone peroxycarboxylic acids and, forcomparison, several prior art peracids are presented below in Table III.

Other determinations were obtained from the above-described test bycalculating data from the plot A/Ao to determine the amount of activeoxygen in the sample after a period of 30 days. The results are reportedin Table III as the percentage of the original amount of active oxygenin the sample.

                  TABLE III                                                       ______________________________________                                                          85% R.H., 39° C.                                                                  % A.sub.o Retained                               Sample              t.sub.50 (days)                                                                        at 30 days                                       ______________________________________                                        Magnesium monoperoxyphthalate                                                                     35       53                                               hexahydrate                                                                   Dodecanediperoxycarboxylic Acid,                                                                  30       50                                               w/boric acid                                                                  n-Decylbutanediperoxoic Acid,                                                                     5-20     <50                                              w/boric acid                                                                  1,4-Phenylenediperoxyacetic Acid,                                                                   12.5   15                                               w/boric acid                                                                  Sulfonyldiperoxypropionic Acid,                                                                   28       41                                               w/boric acid                                                                  Sulfonyldiperoxybenzoic Acid,                                                                              96                                               w/boric acid                                                                  4-Methylsulfonylperoxybenzoic Acid,                                                                        94                                               w/boric acid                                                                  3-Decylsulfonylperoxypropionic Acid,                                                                       92                                               w/boric acid                                                                  ______________________________________                                    

In another procedure the temperature of onset of self-heating for bleachcompounds and formulations thereof was determined by the followingprocedure employing accelerating rate calorimetery (ARC). In thisprocedure samples to be tested are monitored for temperature changes asthey are heated in stepped increments of five degrees centigrade. Aftereach step ten minutes is allowed for thermal equilibrium to occurfollowed by a hold time of twenty minutes at adiabatic conditions. Thismethod continues until the onset of selfheating is observed. The resultsof this test appear in Table IV under the column marked "A.R.C.".Several known prior art bleaches were included for comparison.

Also shown in Table IV are data obtained in a procedure to determine thepercent active oxygen remaining in boric acid stabilized formulations ofcompounds of this invention. In this procedure 100 g of the formulationis placed in an oven held at 50° C. for 7 days. Open polyethylenecontainers are employed to hold the formulations. The percent of theinitial active oxygen remaining in the formulation after 7 days isreported in Table IV under the column marked "Ambient Humidity, 50° C."indicating that the samples were in contact with ambient atmosphereduring the test period.

                  TABLE IV                                                        ______________________________________                                                                     Ambient                                                             A.R.C.    Humidity                                                            Onset of  50° C.                                                       Self-heating                                                                            % A.sub.o Retained                               Sample             (°C.)                                                                            After 7 Days                                     ______________________________________                                        Magnesium monoperoxyphthalate                                                                    78        --                                               hexahydrate                                                                   Dodecanediperoxycarboxylic Acid,                                                                 60        --                                               w/boric acid                                                                  1,4-Phenylenediperoxyacetic Acid                                                                 51        --                                               w/boric acid                                                                  Sulfonyldiperoxypropionic Acid,                                                                  96        85                                               w/boric acid                                                                  Sulfonyldiperoxybenzoic Acid,                                                                    --        99                                               w/boric acid                                                                  ______________________________________                                    

In addition to the compounds of this invention described by the aboveexamples, any number of other compounds are contemplated to be withinthe spirit and scope of this invention. Some examples of such compoundsare represented by the formulae below: ##STR30##

The sulfone peroxycarboxylic acids can be employed alone or be combinedwith other materials in any number of ways to produce formulatedproducts. Examples of such formulated products include but are notlimited to complete laundry detergents, dry bleach formulations, machinedishwashing formulations, bleach releasing articles such as pouches,fabric sheets, and the like, bleaching formulations for use in drycleaning operations, products for use in textile or paper manufacture,hard surface cleaners, and the like. Among other known ingredientstypically employed in such formulations are stabilizers, chelatingagents, solubilizers, surfactants, diluents, detergent builders,fragrances, pH adjustment agents, abrasives, optical brighteners,coloring agents, exotherm control agents, solvents, encapsulationagents, enzymes, etc. All such formulations which comprise a bleacheffective amount of a sulfone peroxycarboxylic acid are within the scopeof this invention. It is obvious that materials selected to provide theabove formulations must be compatible with peroxycarboxylic acids ofthis invention or means must be taken to segregate the material from thebleach.

Typical pH adjustment agents are used to alter or maintain aqueoussolutions of the instant compositions during use within the 5 to 10 pHrange in which peroxyacid bleaching agents are generally most effective.Depending upon the nature of other optional composition ingredients, pHadjustment agents can be either of the acid or base type. Examples ofacidic pH adjustment agents designed to compensate for the presence ofother highly alkaline materials include normally solid organic andinorganic acids, acid mixtures and acid salts. Examples of such acidicpH adjustment agents include citric acid, glycolic acid, sulfamic acid,sodium bisulfate, potassium bisulfate, ammonium bisulfate and mixturesof citric acid and lauric acid. Citric acid is preferred by virtue ofits low toxicity and hardness sequestering capability.

Optional alkaline pH adjustment agents include the conventional alkalinebuffering agents. Examples of such buffering agents include such saltsas carbonates, bicarbonates, phosphates, silicates and mixtures thereof.

Since the proxyacid compounds used in the compositions of the presentinvention are subject to the loss of available oxygen when contacted byheavy metals, it is desirable to include a chelating agent in thecompositions. Such agents are preferably present in an amount rangingfrom about 0.005% to about 1.0% based on the weight of the composition.The chelating agent can be any of the well known agents, but certain arepreferred. U.S. Pat. No. 3,442,937, May 6, 1969, to Sennewald et al,discloses a chelating system comprising quinoline or a salt thereof, analkali metal polyphosphate, and, optionally, a synergistic amount ofurea. U.S. Pat. No. 2,838,459, July 10, 1958, to Sprout, Jr., disclosesa variety of polyphosphates as stabilizing agents for peroxide baths.These materials are useful herein. U.S. Pat. No. 3,192,255, June 29,1965, to Cann, discloses the use of quinaldic acid to stabilizepercarboxylic acids. This material, as well as picolinic acid anddipicolinic acid, would also be useful in the compositions of thepresent invention. A preferred chelating system for the presentinvention is the alkali metal polyphosphate system.

In addition to the above-mentioned chelating systems to tie up heavymetals in the peroxyacid compositions, coating materials (encapsulatingagents) may also be used as stabilizers to extend the shelf life of drygranular compositions. Such coating materials may be in general, acids,esters, and hydrocarbons and include such things as wide varieties offatty acids, derivatives of fatty alcohols such as esters andhydrocarbon oils and waxes. These materials aid in preventing moisturefrom reaching the peroxyacid compound. Secondly, the coating may be usedto segregate the peroxycarboxylic compound from other agents which maybe present in the composition and adversely affect theperoxycarboxylic's stability. The amount of the coating material used isgenerally from about 2.5% to about 15% based on the weight of theperoxycarboxylic acid compound.

It is known to combine peroxycarboxylic acids with exotherm controlagents to prevent runaway reaction in the event of overheating, etc. Theuse of boric acid as an exotherm control agent has been described inU.S. Pat. No. 4,100,095, issued July 11, 1978 to Hutchins et al. Otherpossible exotherm control agents include hydrates of salts such asmagnesium sulfate, calcium sodium sulfate, magnesium nitrate, potassiumaluminum sulfate, and aluminum sulfate, and the like as disclosed inU.S. Pat. No. 3,770,816, issued Nov. 6, 1973 to Nielson. Such materialsmay be employed in conjunction with sulfone peroxycarboxylic acids.

Agents which improve the solubility of the sulfone peroxycarboxylic acidproduct such as sodium sulfate, starch, cellulose derivatives,surfactants, etc., are also advantageously used herein. These agents canbe called solubilizers and are generally used in an amount of from about10% to about 200% based on the weight of the peroxyacid.

Optional materials for the instant bleaching compositions can includesuch standard detergent adjuvants as surfactants and builders. Optionalsurfactants are selected from the group consisting of organic anionic,nonionic, ampholytic, and zwitterionic surfactants and mixtures thereof.Optional builder materials include any of the conventional organic andinorganic builder salts including carbonates, silicates, acetates,polycarboxylates and phosphates If the instant stabilized bleachingcompositions are employed as part of a conventional fabric launderingdetergent composition, the instant bleaching system generally comprisesfrom about 1% to about 40% by weight of such conventional detergentcompositions. Conversely, the instant bleaching compositions canoptionally contain from about 60% to about 99% by weight of conventionalsurfactant and builder materials. Further examples of suitablesurfactants and builders are given below.

Water-soluble salts of the higher fatty acids, i.e., "soaps", are usefulas the anionic surfactant herein. This class of surfactants includesordinary alkali metal soaps such as the sodium, potassium, ammonium andalkanolammonium salts of higher fatty acids containing from about 8 toabout 24 carbon atoms and preferably from about 10 to about 20 carbonatoms. Soaps can be made by direct saponification of fats and oils or bythe neutralization of free fatty acids. Particularly useful are thesodium and potassium salts of the mixtures of fatty acids derived fromcoconut oil and tallow, i.e., sodium or potassium tallow and coconutsoaps.

Another class of anionic surfactants includes water-soluble salts,particularly the alkali metal, ammonium and alkanolammonium salts, oforganic sulfuric reaction products having in their molecular structurean alkyl group containing from about 8 to about 22 carbon atoms and asulfonic acid or sulfuric acid ester group. (Included in the term"alkyl" is the alkyl portion of acyl groups.) Examples of this group ofsynthetic surfactants which can be used in the present detergentcompositions are the sodium and potassium alkyl sulfates, especiallythose obtained by sulfating the higher alcohols (C₈ -C₁₈ carbon atoms)produced by reducing the glycerides of tallow or coconut oil; and sodiumand potassium alkyl benzene sulfonates, in which the alkyl groupcontains from about 9 to about 15 carbon atoms in straight chain orbranched chain configuration, e.g., those of the type described in U.S.Pat. Nos. 2,220,099, and 2,477,383, incorporated herein by reference.

Other anionic surfactant compounds useful herein include the sodiumalkyl glyceryl ether sulfonates, especially those ethers or higheralcohols derived from tallow and coconut oil; sodium coconut oil fattyacid monoglyceride sulfonates and sulfates; and sodium or potassiumsalts of alkyl phenol ethylene oxide ether sulfate containing about 1 toabout 10 units of ethylene oxide per molecule and wherein the alkylgroups contain about 8 to about 12 carbon atoms.

Other useful anionic surfactants herein include the water-soluble saltsof esters of α-sulfonated fatty acids containing from about 6 to 20carbon atoms in the ester group; water-soluble salts of2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbonatoms in the acyl group and from about 9 to about 23 carbon atoms in thealkane moiety; alkyl ether sulfates containing from about 10 to 20carbon atoms in the alkyl group and from about 1 to 30 moles of ethyleneoxide; water-soluble salts of olefin sulfonates containing from about 12to 24 carbon atoms; and β-alkyloxy alkane sulfonates containing fromabout 1 to 3 carbon atoms in the alkyl group and from about 8 to 20carbon atoms in the alkane moiety.

Preferred water-soluble anionic organic surfactants herein includelinear alkyl benzene sulfonates containing from about 11 to 14 carbonatoms in the alkyl group; the tallow range alkyl sulfates; the coconutrange alkyl glyceryl sulfonates; and alkyl ether sulfates wherein thealkyl moiety contains from about 14 to 18 carbon atoms and wherein theaverage degree of ethoxylation varies between 1 and 6.

Specific preferred anionic surfactants for use herein include: sodiumlinear C₁₀ -C₁₂ alkyl benzene sulfonate; triethanolamine C₁₀ -C₁₂ alkylbenzene sulfonate; sodium tallow alkyl sulfate; sodium coconut alkylglyceryl ether sulfonate; and the sodium salt of a sulfated condensationproduct of tallow alcohol with from about 3 to about 10 moles ofethylene oxide.

It is to be recognized that any of the foregoing anionic surfactants canbe used separately herein or as mixtures.

Nonionic surfactants include the watersoluble ethoxylates of C₁₀ -C₂₀aliphatic alcohols and C₆ -C₁₂ alkyl phenols. Many nonionic surfactantsare especially suitable for use as suds controlling agents incombination with anionic surfactants of the type disclosed herein.

Semi-polar surfactants useful herein include water-soluble amine oxidescontaining one alkyl moiety of from about 10 to 28 carbon atoms and 2moieties selected from the group consisting of alkyl groups andhydroxyalkyl groups containing from 1 to about 3 carbon atoms;watersoluble phosphine oxides containing one alkyl moiety of about 10 to28 carbon atoms and 2 moieties selected from the group consisting ofalkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbonatoms; and water-soluble sulfoxides containing one alkyl moiety of fromabout 10 to 28 carbon atoms and a moiety selected from the groupconsisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbonatoms.

Ampholytic surfactants include derivatives of aliphatic or aliphaticderivatives of heterocyclic secondary and tertiary amines in which thealiphatic moiety can be straight chain or branched and wherein one ofthe aliphatic substituents contains from about 8 to 18 carbon atoms andat least one aliphatic substituent contains an anionicwater-solubilizing group.

Zwitterionic surfactants include derivatives of aliphatic quaternaryammonium, phosphonium and sulfonium compounds in which the aliphaticmoieties can be straight or branched chain, and wherein one of thealiphatic substituents contains from about 8 to 18 carbon atoms and onecontains an anionic watersolubilizing group.

The instant granular compositions can also comprise those detergencybuilders commonly taught for use in laundry compositions. Usefulbuilders herein include any of the conventional inorganic and organicwater-soluble builder salts, as well as various water-insoluble andsocalled "seeded" builders.

Inorganic detergency builders useful herein include, for example,water-soluble salts of phosphates, pyrophosphates, orthophosphates,polyphosphates, phosphonates, carbonates, bicarbonates, borates andsilicates. Specific examples of inorganic phosphate builders includesodium and potassium tripolyphosphates, pyrophosphates, andhexametaphosphates. The polyphosphonates specifically include, forexample, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid, and the sodium and potassium salts ofethane-1,1,2-triphosphonic acid. Examples of these and other phosphorusbuilder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030;3,422,021; 3,422,137; 3,400,176 and 3,400,148; incorporated herein byreference. Sodium tripolyphosphate is an especially preferred,water-soluble inorganic builder herein.

Non-phosphorus containing sequestrants can also be selected for useherein as detergency builders. Specific examples of non-phosphorus,inorganic builder ingredients include water-soluble inorganic carbonate,bicarbonate, borate and silicate salts.

Water-soluble, organic builders are also useful herein. For example, thealkali metal, ammonium and substituted ammonium polyacetates, polyacetalcarboxylates, carboxylates, polycarboxylates, succinates, andpolyhydroxysulfonates are useful builders in the present compositionsand processes. Specific examples of the polyacetate and polycarboxylatebuilder salts include sodium, potassium, lithium, ammonium andsubstituted ammonium salts of ethylene diamine tetraacetic acid,nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzenepolycarboxylic acids, and citric acid.

Highly preferred non-phosphorous builder materials (both organic andinorganic) herein include sodium carbonate, sodium bicarbonate, sodiumsilicate, sodium citrate, sodium oxydisuccinate, sodium mellitate,sodium nitrilotriacetate, and sodium ethylenediaminetetraacetate, andmixtures thereof.

Another type of detergency builder material useful in the presentcompositions and processes comprises a water-soluble material capable offorming a water-insoluble reaction product with water hardness cationsin combination with a crystallization seed which is capable of providinggrowth sites for said reaction product.

Specific examples of materials capable of forming the water-insolublereaction product include the water-soluble salts of carbonates,bicarbonates, sesquicarbonates, silicates, aluminates and oxalates. Thealkali metal, especially sodium, salts of the foregoing materials arepreferred for convenience and economy.

Another type of builder useful herein includes various substantiallywater-insoluble materials which are capable of reducing the hardnesscontent of laundering liquors, e.g., by ion-exchange processes. Examplesof such builder materials include the phosphorylated cloths disclosed inU.S. Pat. No. 3,424,545, Bauman, issued Jan. 28, 1969, incorporatedherein by reference.

The complex aluminosilicates, i.e., zeolite type materials, are usefulpresoaking/washing adjuvants herein in that these materials softenwater, i.e., remove Ca++ hardness. Both the naturally occurring andsynthetic "zeolites", especially zeolite A and hydrated zeolite Amaterials, are useful for this builder/softener purpose. A descriptionof zeolite materials and a method of preparation appears in Milton, U.S.Pat. No. 2,882,243, issued Apr. 14, 1959, incorporated herein byreference.

Bleaching compositions of this invention are normally solid therebyfacilitating preparation of detergent compositions. The novel bleachesof this invention can be admixed with other granules of optionalbleaching or detergent composition materials. Actual particle size ofeither the bleach-containing granules or optional granules of additionalmaterial is not critical. If, however, compositions are to be realizedhaving commercially acceptable flow properties, certain granule sizelimitations are highly preferred. In general, all granules of theinstant compositions preferably range in size from about 100 microns to3000 microns, more preferably from about 100 microns to 1300 microns.

Additionally, flowability is enhanced if particles of the presentinvention are of approximately the same size. Therefore, preferably theratio of the average particle sizes of the bleach-containing granulesand optional granules of other materials varies between 0.5:1 and 2.0:1.

Bleaching compositions of the present invention are utilized bydissolving them in water in an amount sufficient to provide from about1.0 ppm to 50 ppm available oxygen in solution. Generally, this amountsto about 0.0001% to 0.005% by weight of active oxygen in solution.Fabrics to be bleached are then contacted with such aqueous bleachingsolutions.

Among the sulfone peroxycarboxylic acids of this invention, the degreeof bleaching activity per unit weight of active oxygen can vary widely.Preferred embodiments are those with a relatively high level ofbleaching activity per unit weight of active oxygen, since smalleramounts of such compounds can be used to achieve a given degree ofbleaching. Embodiments which sustain this high performance at relativelylow bleaching temperatures, i.e. ≦60° C. are particularly preferred.Also preferred are embodiments with a relatively high weight percentageof active oxygen in the sulfone peroxycarboxylic acid molecule, sincesuch embodiments tend to consume a smaller weight of raw materials perunit of active oxygen present.

Thermal and moisture stability of the peroxyacid bleaches are importantfor safety, storage and shelflife considerations. Many prior artperoxycarboxylic acids that have good bleaching performance have notbeen commercialized due to poor thermal and moisture stabilityproperties. However, the sulfone peroxyacids of this invention haveshown surprisingly high thermal and moisture stabilities.

While the degree of molecular stability (as reflected in such propertiesas storage stability or thermal stability in various formulations, etc.)will vary among sulfone peroxycarboxylic acids, they are usually morestable than otherwise similar peroxycarboxylic acids which lack thesulfone group. Similarly the tendency to cause dye damage will vary butwill usually be reduced by the presence of one or more sulfone groups.Preferred embodiments are those exhibiting relatively high degrees ofstability and relatively low degrees of dye damage. Particularlypreferred are embodiments which exhibit in a single molecule or reactionproduct a combination of high stability, low dye damage, and highbleaching activity per unit weight.

Depending upon the specific intended use, such properties as particlesize, appearance, and odor of the sulfone peroxycarboxylic acids of thisinvention may be important. In most embodiments, these compounds can beproduced as white, relatively odorless powders of relatively smallparticle size, and such embodiments are usually preferred. If desired,particle size distribution can be adjusted by such known methods asmilling, screening, or agglomeration.

Included within the scope of this invention are various bleachingprocesses in which sulfone peroxycarboxylic acids are employed ineffective amounts as active bleaching ingredients. Generally, in suchprocesses, articles to be bleached are contacted in an aqueous mediumwith a bleach effective amount of one or more sulfone peroxycarboxylicacids. Other conditions important in such processes include temperature,pH, contact time, selection and level of various ingredients presentduring bleaching, agitation, etc. Optimization of such conditions can beaccomplished for each particular case by routine experimentation in viewof this disclosure. Particularly preferred are processes in which thetemperature is fairly low, i.e. not above 60° C., since such processesprovide rapid and effective bleaching while minimizing adverse effectsassociated with higher temperatures such as dye damage, fabricshrinkage, high energy consumption, and weakening of fabrics or otherarticles subjected to bleaching.

Although the invention has been described in terms of specificembodiments which are set forth in considerable detail, it should beunderstood that this description is by way of illustration only and thatthe invention is not necessarily limited thereto since alternativeembodiments and operating techniques will become apparent to thoseskilled in the art in view of this disclosure. Accordingly,modifications are contemplated which can be made without departing fromthe spirit of the described invention.

What is claimed is:
 1. A compound represented by the formula ##STR31##wherein A and B are peroxycarboxylic acid compatible organic moietiesbonded to the sulfur atom by a carbon atom, each of A and B containingfrom 1 to 4 ##STR32## groups bonded to carbon atoms.
 2. A compound ofclaim 1 wherein A and B contain a total of two peroxycarboxylic acidgroups.
 3. A compound of claim 1 wherein at least one of A and B is anaryl group.
 4. A compound of claim 3 wherein the aryl group is aperoxybenzoic acid group.
 5. A compound of claim 1 wherein thetheoretical active oxygen content is above about 5.42 percent.
 6. Acompound of claim 1 in the form of a particulate solid.
 7. A compound ofclaim 1 wherein A and B are the same.
 8. A compound of claim 1 wherein Aand B are dissimilar.
 9. A compound represented by the formula ##STR33##wherein X and Y are hydrocarbyl groups, each of X and Y beingsubstituted with a total of from 1 to 4 ##STR34## groups.
 10. A compoundof claim 9 wherein X and Y are the same.
 11. A compound of claim 9wherein X and Y are different.
 12. A compound of claim 9 wherein each ofX and Y are aryl.
 13. A compound of claim 12 wherein the aryl is phenyl.14. A compound of claim 9 wherein X and Y are alkyl.
 15. A compound ofclaim 12 wherein each aryl group is the same.
 16. A compound of claim 14wherein the alkyl group has from 1 to 4 carbon atoms.
 17. A compound ofclaim 14 wherein the alkyl is ethyl.
 18. A compound of claim 11 whereinX is alkyl having from 9 to 12 carbon atoms and Y is alkyl having from 1to 4 carbon atoms.
 19. A compound of claim 9 wherein X is cyclohexyl andY is ethyl.
 20. A compound of claim 9 wherein X is methyl and Y isphenyl.
 21. A compound of claim 9 wherein X and Y are peroxybenzoic acidgroups.
 22. A compound of claim 9 wherein X is an alkyl group and Y is aperoxybenzoic acid group.
 23. A compound of claim 22 wherein the alkylgroup contains from 2 to 10 carbon atoms.
 24. A compound of claim 23wherein the alkyl group is ethyl.
 25. A bleaching detergent compositioncomprising an effective amount of a compound of claim 1 and a detergentsurfactant.
 26. A composition of claim 25 further including a detergentbuilder.
 27. A composition of claim 25 wherein the surfactant isselected from anionic, nonionic and zwitterionic surfactants.
 28. Acomposition of claim 25 wherein A or B are independently selected fromthe group consisting of a cyclic, linear or branched alkyl group, anaryl group, an alkylaryl group, an aromatic heterocyclic group, apolyaryl group consisting of from 2 to 4 annelated enzenoid rings, andmixtures thereof containing up to about 18 carbon atoms and beingoptionally additionally substituted with halogen, sulfonate, nitro,carboxylate, carboxylic acid, C₁ -₅ alkyl, hydroyx, trifluoromethyl,aryl, sulfone, amine oxide, amide, ester or sulfate groups, or mixturesthereof.
 29. A composition of claim 25 wherein A and B are the same. 30.A composition of claim 25 wherein A and B are dissimilar.
 31. Acomposition of claim 25 wherein A and B contain a total of two ##STR35##groups.
 32. A composition of claim 25 wherein A is an alkyl group and Bis an aryl group.
 33. A bleaching detergent composition comprising aneffective amount of a compound of claim 9 and a detergent surfactant.34. A composition of claim 33 wherein X and Y are the same.
 35. Acomposition of claim 33 wherein X and Y are different.
 36. A compositionof claim 33 wherein each of X and Y are aryl.
 37. A composition of claim36 wherein the aryl is phenyl.
 38. A composition of claim 33 wherein Xand Y are alkyl.
 39. A composition of claim 37 wherein each aryl groupis the same.
 40. A composition of claim 38 whereien the alkyl group hasfrom 1 to 4 carbon atoms.
 41. A composition of claim 38 wherein thealkyl is ethyl.
 42. A composition of claim 35 wherein X is alkyl havingfrom 9 to 12 carbon atoms and Y is alkyl having from 1 to 4 carbonatoms.
 43. A composition of claim 33 wherein X is cyclohexyl and Y isethyl.
 44. A composition of claim 33 wherein X is methyl and Y isphenyl.
 45. A dry bleach composition comprising, by weight, from about 0percent to about 50 percent detergent surfactant, detergent builder or amixture thereof and from about 1 percent to about 50 percent of acompound of claim
 1. 46. A dry bleach composition comprising, by weight,from about 0 to about 50 percent detergent surfactant, detergent builderor a mixture thereof and from about 1 percent to about 50 percent of acompound of claim
 9. 47. A process for bleaching articles comprisingcontacting articles to be bleached with an aqueous medium containing ableach effective amount of a compound represented by the formula:##STR36## wherein A and B are peroxycarboxylic acid compatible organicmoieties bonded to the sulfur atom by a carbon atom, each of A and Bcontaining at least one ##STR37## group bonded to carbon atoms.
 48. Aprocess of claim 47 wherein A and B are the same.
 49. A process of claim47 wherein A and B are dissimilar.
 50. A process of claim 47 wherein Aand B contain a total of two ##STR38## groups.
 51. A process of claim 47wherein A is an alkyl group and B is an aryl group containing at leastone ##STR39## group.
 52. A process for bleaching articles comprisingcontacting articles to be bleached with an aqueous medium containing ableach effective amount of a compound represented by the formula:##STR40## wherein X and Y are hydrocarbyl groups, each of X and Y beingsubstituted with at least one ##STR41## group.
 53. A process of claim 52wherein X and Y are the same.
 54. A process of claim 52 wherein X and Yare different.
 55. A process of claim 52 wherein each of X and Y arearyl.
 56. A process of claim 52 wherein the aryl is phenyl.
 57. Aprocess of claim 52 wherein X and Y are alkyl.
 58. A process of claim 57wherein the alkyl group has from 1 to 4 carbon atoms.
 59. A process ofclaim 58 wherein the alkyl is ethyl.
 60. A process of claim 54 wherein Ais alkyl having from 9 to 12 carbon atoms and B is alkyl having from 1to 4 carbon atoms.
 61. A process of claim 52 wherein X is cyclohexyl andY is ethyl.
 62. A process of claim 52 wherein X is methyl and Y isphenyl.